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| United States Patent |
5,532,344
|
|
Himeno
, et al.
|
July 2, 1996
|
Process for producing a monoazodye by diazo-coupling of a p-nitroanaline
derivative with a N,N-substituted analine derivative
Abstract
A process for producing a monoazodye of the following formula (III):
##STR1##
wherein X.sup.1 is nitro or halogen, X.sup.2 is halogen, R.sup.1 is lower
alkoxy, R.sup.2 is lower alkyl, each of R.sup.3 and R.sup.4, which are
independent of each other, is alkyl, cyanoalkyl or alkylcarbonyloxyalkyl,
and each of m and n, which are independent of each other, is 0 or 1, which
comprises diazotizing an aniline derivative of the following formula (I):
##STR2##
wherein X.sup.1 and X.sup.2 are as defined above, followed by coupling
with an aniline derivative of the following formula (II):
##STR3##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, m and n are as defined above,
wherein a reaction mixture obtained by the coupling reaction is
heat-treated in the presence of a polyoxyethylene higher fatty acid ester
type nonionic surfactant, followed by filtration to obtain said monoazo
compound in the form of a cake.
| Inventors:
|
Himeno; Kiyoshi (Munakata, JP);
Hihara; Toshio (Kitakyushu, JP);
Hamano; Yoshiharu (Kitakyushu, JP);
Kubo; Shinji (Nakama, JP)
|
| Assignee:
|
Dystar Japan Ltd. (Osaka, JP)
|
| Appl. No.:
|
038813 |
| Filed:
|
March 29, 1993 |
Foreign Application Priority Data
| Apr 02, 1992[JP] | 4-108428 |
| Apr 16, 1992[JP] | 4-096823 |
| Apr 20, 1992[JP] | 4-099953 |
| Current U.S. Class: |
534/581; 534/575; 534/887 |
| Intern'l Class: |
C09B 041/00; C09B 029/085; C09B 067/10 |
| Field of Search: |
534/581,887,575
|
References Cited
U.S. Patent Documents
| 2812321 | Nov., 1957 | Eberhart et al. | 534/565.
|
| 4252718 | Feb., 1981 | Atherton et al. | 534/582.
|
| 4785082 | Nov., 1988 | Weide et al. | 534/581.
|
| 4795807 | Jan., 1989 | Buhler et al. | 534/575.
|
| 4960435 | Oct., 1990 | Tunoda et al. | 534/575.
|
| 5209758 | May., 1993 | Traber et al. | 8/526.
|
| Foreign Patent Documents |
| 0363730 | Apr., 1990 | EP.
| |
| 0436867 | Jul., 1991 | EP.
| |
| 2057480 | May., 1971 | FR.
| |
| 2290473 | Jun., 1976 | FR.
| |
| 3234335 | Mar., 1984 | DE | 534/581.
|
| 208477 | May., 1984 | DE.
| |
| 59-51280 | Mar., 1984 | JP | 534/581.
|
| 2193218 | Feb., 1988 | GB.
| |
Other References
Chemical Abstracts, vol. 112, No. 20, May 14, 1990, AN 181386e, G. N.
Koshel, "Manufacture of Benzanilide Monoazo Pigments".
Chemical Abstracts, vol. 76, No. 18, May 1, 1972, AN 101209z, F. Vyskocil,
et al., "Disperse Azo Dyes".
Chemical Abstracts, vol. 107, No. 10, Sep. 1987, AN 79478w, H. W. Modrow,
et al., "Color-Stable, Easily Ground C.I. Disperse Orange 30".
Chemical Abstracts, vol. 90, No. 14, Apr. 2, 1979, AN 105628x, V. Vanc, et
al., "Stabilized Disperse Yellow 3".
Nippon, Chemical Abstracts, 102:222144 (1985).
English Translation of JP 59-51280, Mar. 24, 1984.
Derwent Abstract of DD 208447, May 2, 1984.
Derwent Abstract of JP 59-51280 Mar. 24, 1984.
|
Primary Examiner: Powers; Fiona T.
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier & Neustadt
Claims
We claim:
1. A process for producing a monoazo dye of the following formula (III):
##STR17##
wherein X.sup.1 is nitro or halogen, X.sup.2 is halogen, R.sup.1 is lower
alkoxy, R.sup.2 is lower alkyl, each of R.sup.3 and R.sup.4, which are
independent of each other, is alkyl, cyanoalkyl or alkylcarbonyloxyalkyl,
and each of m and n, which are independent of each other, is 0 or 1, which
comprises diazotizing an aniline derivative of the following formula (I):
##STR18##
wherein X.sup.1 and X.sup.2 are as defined above, followed by coupling, in
an aqueous medium under acidic conditions and in the presence of a
polyoxyethylene higher fatty acid ester nonionic surfactant, with an
aniline derivative of the following formula (II):
##STR19##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, m and n are as defined above,
wherein a reaction mixture obtained by the coupling reaction is
heat-treated in the presence of said polyoxyethylene higher fatty acid
ester nonionic surfactant, followed by filtration to obtain said
monoazodye in the form of a cake, and wherein the nonionic surfactant is
of the formula:
R--COO--(C.sub.2 H.sub.4 O).sub.n H
where R is a C.sub.10 -C.sub.20 saturated or unsaturated aliphatic
hydrocarbon group and n is a positive integer.
2. The process according to claim 1, wherein X.sup.1 is nitro, X.sup.2 is
chlorine or bromine, R.sup.1 is methoxy or ethoxy, R.sup.2 is methyl, each
of R.sup.3 and R.sup.4 is
##STR20##
and each of m and n is 1.
3. The process according to claim 1, wherein X.sup.1 is nitro, X.sup.2 is
chlorine or bromine, R.sup.2 is methyl each of R.sup.3 and R.sup.4 is
C.sub.1-4 lower alkyl, m is 0, and n is 1.
4. The process according to claim 3, wherein each of R.sup.3 and R.sup.4 is
ethyl.
5. The process according to claim 1, wherein each of X.sup.1 and X.sup.2 is
halogen, R.sup.3 is cyanoalkyl, R.sup.4 is alkyl and each of m and n is 0.
6. The process according to claim 5, wherein R.sup.3 is cyanoethyl, and
R.sup.4 is ethyl.
7. The process according to claim 1, wherein R is a C.sub.16 -C.sub.19
saturated or unsaturated aliphatic hydrocarbon group.
8. The process according to claim 1, wherein the polyoxyethylene higher
fatty acid ester type nonionic surfactant has a HLB of from 11 to 16.
9. The process according to claim 8, wherein the nonionic surfactant has a
HLB of from 12 to 15.
10. The process according to claim 1, wherein the nonionic surfactant is
used in an amount of from 1 to 10 wt %, based on the monoazo compound to
be produced.
11. The process according to claim 10, wherein the nonionic surfactant is
used in an amount of from 2 to 5 wt %, based on the monoazo compound to be
produced.
12. The process according to claim 1, wherein the heat treatment after the
coupling reaction is conducted by stirring at a temperature of from
50.degree. to 90.degree. C. for from 0.5 to 3 hours.
13. The process according to claim 1, wherein the coupling reaction is
conducted at a temperature of from -10.degree. to +20.degree. C.
14. The process according to claim 1, wherein said nonionic surfactant is
selected from the group consisting of polyoxyethylene n-hexadecanoic acid
ester, polyoxyethylene n-heptadecanoic acid ester, polyoxyethylene
n-octadecanoic acid ester, polyoxyethylene n-nonadecanoic acid ester,
polyoxyethylene-9-hexadecenoic acid ester, polyoxyethylene-6-octadecenoic
acid ester, polyoxyethylene-9-octadecenoic acid ester,
polyoxyethylene-9,12-octadecadienoic acid ester and polyoxyethylene
dodecanoic acid ester.
15. The process according to claim 1, wherein said coupling reaction
conducted under acidic conditions is conducted in the presence of sulfuric
acid.
Description
The present invention relates to a process for producing a monoazodye. More
particularly, it relates to a process for producing a monoazodye, whereby
the productivity is improved.
Monoazo compounds of the following structural formulas have long been known
as disperse dyes.
##STR4##
In the above formulas, X is halogen.
These monoazo compounds can be prepared by diazotizing the respective
anilines as their diazo components by conventional methods, followed by
coupling witch the respective aniline derivatives as their coupling
components in an aqueous medium. However, the cakes thereby obtained have
a drawback that when they are used as disperse dyes, the dispersibility as
dyes and the stability with time are poor.
Therefore, it has been common to employ a method wherein a mixture obtained
by the coupling reaction is once subjected to filtration, washed with
water and again heat-treated in an aqueous medium at a temperature of from
90.degree. to 95.degree. C. for from 3 to 6 hours. The reason why the heat
treatment is conducted after filtration is that if the reaction mixture is
subjected directly to heat treatment, the ester groups of the dye tend to
be hydrolyzed.
By such heat treatment, the crystalline condition is improved favorably,
although no crystal transition of the monoazo compound will take place.
However, the above method has the following problems from the industrial
viewpoint.
1. The filtration property of the cake is poor, and the ester groups of the
dye tend to undergo hydrolysis during the filtration of the cake. Further,
a filtration apparatus with a large filtration capacity is required.
2. Heat treatment of the cake is required to attain good dispersibility of
the dye. Before the heat treatment, an filtration operation is required.
Thus, two steps are required for the production of the cake, whereby the
productivity is very poor.
It is an object of the present invention to solve such problems inherent to
the prior art and to provide a process for producing a monoazodye, whereby
the productivity is improved.
The present invention provides a process for producing a monoazodye of the
following formula (III):
##STR5##
wherein X.sup.1 is nitro or halogen, X.sup.2 is halogen, R.sup.1 is lower
alkoxy, R.sup.2 is lower alkyl, each of R.sup.3 and R.sup.4, which are
independent of each other, is alkyl, cyanoalkyl or alkylcarbonyloxyalkyl,
and each of m and n, which are independent of each other, is 0 or 1, which
comprises diazotizing an aniline derivative of the following formula (I):
##STR6##
wherein X.sup.1 and X.sup.2 are as defined above, followed by coupling
with an aniline derivative of the following formula (II):
##STR7##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, m and n are as defined above,
wherein a reaction mixture obtained by the coupling reaction is
heat-treated in the presence of a polyoxyethylene higher fatty acid ester
type nonionic surfactant, followed by filtration to obtain said monoazo
compound in the form of a cake.
Now, the present invention will be described in detail.
The aniline derivative of the formula (I) includes, for example,
2,4-dinitro-6-chloroaniline, 2,4-dinitro-6-bromoaniline,
2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitroaniline,
2,6-difluoro-4-nitroaniline, 2,6-diiodo-4-nitroaniline and
2-bromo-6-chloro-4-nitroaniline.
The diazotization reaction is conducted usually by dissolving the aniline
derivative of the formula (I) in nitrosyl sulfuric acid at a temperature
of from 10.degree. to 40.degree. C., preferably from 20.degree. to
30.degree. C., and stirring the solution for from 3 to 5 hours.
After completion of the diazotization reaction, the diazotized aniline
derivative is subjected to the coupling reaction with an aniline
derivative of the above formula (II).
In the formula (II), R.sup.1 is lower alkoxy such as methoxy or ethoxy.
R.sup.2 is lower alkyl such as methyl or ethyl, and methyl is preferred
Each of R.sup.3 and R.sup.4, which are independent of each other, is alkyl
such as methyl, ethyl, propyl or butyl, preferably lower alkyl, cyanoalkyl
such as cyanoethyl or cyanopropyl, preferably cyano lower alkyl,
alkylcarbonyloxyalkyl such as methylcarbonyloxyethyl,
ethylcarbonyloxyethyl, methylcarbonyloxypropyl or ethylcarbonyloxypropyl,
preferably lower alkylcarbonyloxy lower alkyl. Each of m and n, which are
independent of each other, is 0 or 1. Here, "lower" means C.sub.1-4. Among
aniline derivatives of the formula (II), particularly preferred are the
following compounds.
##STR8##
The coupling reaction is conducted usually in an aqueous medium under an
acidic condition. For example, the coupling reaction can be conducted by
dissolving the compound of the formula (II) in an aqueous medium such as
hydrochloric acid, sulfuric acid or acetic acid and mixing thereto the
diazotized solution obtained by the above-mentioned diazotization reaction
under stirring.
For the coupling reaction, it is preferred to add a small amount of a
nitrous acid-removing agent such as sulfamic acid.
The coupling reaction is conducted usually at a temperature of from
-10.degree. to +20.degree. C., preferably from -5.degree. to +5.degree.
C., and the reaction time is usually from 1 to 10 hours.
By the coupling reaction, a reaction mixture containing crystals of the
monoazo compound of the above formula (III), is obtained.
Among monoazo compounds of the formula (III), preferred are the following
compounds.
##STR9##
In the above formulas, each of X.sup.13, X.sup.21, X.sup.22 and X.sup.23
is chlorine or bromine, and R.sup.11 is methoxy or ethoxy.
In the present invention, the reaction mixture containing crystals of this
monoazo compound, is subjected to heat treatment in the presence of the
specific surfactant. If a cake is recovered by filtration without
conducting the heat treatment, the volume of the cake will be very large,
and the filtration property tends to be poor, whereby the compound tends
to undergo hydrolysis during the filtration. Further, a powdery dye
obtained by finely pulverizing the mixture by a pulverizer such as a sand
mill by using an anion dispersant, will be poor in the dispersibility and
the stability with time.
The above heat treatment is conducted usually by stirring at a temperature
of from 50.degree. to 90.degree. C., preferably from 50.degree. to
70.degree. C., for from 0 5 to 3 hours, preferably from 1 to 2 hours. If
the heating temperature is too low, no adequate effect of the heat
treatment will be obtained. On the other hand, if the heating temperature
is too high, decomposition of the dye tends to take place, such being
undesirable. If the heating time is too short, no adequate effect of the
heat treatment will be obtained, and if it is too long, such is
uneconomical and undesirable.
The feature of the present invention resides in the presence of a
polyoxyethylene higher fatty acid ester type nonionic surfactant during
the above heat treatment. Namely, by the presence of this surfactant, it
will be possible to continuously heat-treat the mixture after completion
of the coupling reaction, and it is possible to improve the filtration
property of the heat-treated mixture and to reduce the volume of the cake,
whereby filtration of the cake can be efficiently conducted. Besides, the
obtained compound will have good stability with time as a disperse dye.
The polyoxyethylene higher fatty acid ester type nonionic surfactant to be
used in the present invention is usually an ester of a C.sub.11-21
saturated or unsaturated aliphatic acid with a polyoxyethylene glycol and
is represented by the following formula (IV):
R--COO--(C.sub.2 H.sub.4 O).sub.n --H (IV)
wherein R is a C.sub.10-20 saturated or unsaturated aliphatic hydrocarbon
group, and n is a positive integer.
The higher fatty acid constituting the nonionic surfactant is preferably a
C.sub.16-19 aliphatic acid. Specifically, it may be n-hexadecanoic acid
(C.sub.15 H.sub.31 COOH), n-heptadecanoic acid (C.sub.16 H.sub.33 COOH),
n-octadecanoic acid (C.sub.17 H.sub.35 COOH), n-nonadecanoic acid
(C.sub.18 H.sub.37 COOH), 9-hexadecenoic acid ((C.sub.15 H.sub.29 COOH),
6-octadecenoic acid (C.sub.17 H.sub.33 COOH), 9-octadecenoic acid
(C.sub.17 H.sub.33 COOH) or 9,12-octadecadienoic acid (C.sub.17 H.sub.31
COOH).
On the other hand, the polyoxyethylene glycol is preferably the one having
a molecular weight such that the nonionic surfactant formed by
esterification will have a HLB (hydrophilic-lipophilic balance) within a
range of from 11 to 16, preferably from 12 to 15.
Here, the HLB (hydrophilic-lipophilic balance) is an index showing the
molecular weight ratio of the hydrophilic moiety and the lipophilic moiety
of the surfactant and is represented by the following formula.
HLB=(E+P)/5
where E is the weight % of polyoxyethylene in the molecule, and P is the
weight % of polyhydric alcohol in the molecule.
The above nonionic surfactant is used usually in an amount of from 1 to 10
wt %, preferably from 2 to 5 wt %, based on the monoazo compound to be
produced. If the amount of the nonionic surfactant is too small, no
adequate effect for solving the problem will be obtained. On the other
hand, if the amount is too large, no additional effect will be obtained,
and such is not economical. Therefore, it is advisable that the amount is
within the above range.
The nonionic surfactant may be added to the reaction mixture after
completion of the coupling reaction. However, if the nonionic surfactant
is present during the coupling reaction, the yield of the coupling
reaction itself may sometimes be improved in addition to the
above-mentioned effects. Therefore, it is particularly preferred that the
nonionic surfactant is present even during the coupling reaction.
The reaction mixture after the above heat treatment, is then filtered by a
conventional method by means of a filtration machine such as a filter
press, a Nutsche funnel or a centrifugal separator, to recover the cake.
In the present invention, the coupling reaction is followed by heat
treatment of the reaction mixture in the presence of a polyoxyethylene
higher fatty acid ester type nonionic surfactant. By the presence of such
a surfactant, heat treatment can be conducted without filtration of the
reaction mixture after the coupling reaction, and thus the productivity is
good.
Further, foaming during the heat treatment can be minimized, whereby
overflow from the reactor can be avoided, and the yield will be improved.
Moreover, the water content in the cake can effectively be reduced, and
the volume of the cake can be reduced, whereby it will be possible to
conduct filtration by a filtration machine having a relatively small
filtration capacity.
The reason why such effects are obtainable, is not known. Heretofore, it
has been believed that when heat-treated under an acidic condition, an
ester type surfactant undergoes hydrolysis and loses its function as a
surfactant. From such a conventional belief, the above-mentioned effects
are peculiar and surprising.
Further, according to the present invention, the dispersibility as a
feature of a disperse dye, will not be impaired. Thus, according to the
process of the present invention, a monoazodye having excellent
dispersibility can be produced under an improved productivity.
Now, the present invention will be described in further detail with
reference to Examples. However, it should be understood that the present
invention is by no means restricted by such specific Examples. In the
Examples, "parts" means "parts by weight".
EXAMPLES 1 to 6 and COMPARATIVE EXAMPLES 1 to 3
Into a 300 ml glass-lined reactor equipped with a stirrer, 75.6 g of 98%
sulfuric acid and 78.8 g of 43% nitrosylsulfuric acid were added, and 68 g
of 2,4-dinitro-6-bromoaniline was added thereto under stirring at a
temperature of from 20.degree. to 25.degree. C., whereupon a diazotization
reaction was conducted at a temperature of from 20.degree. to 25.degree.
C. for 3 hours to obtain a diazotized solution. Into a 4 l cylindrical
beaker with a bottom area of 150 cm.sup.2, 860 ml of water, 25 g of acetic
acid, 93.5 g of N,N-bis(acetoxyethyl)amino-2-methoxy-5-acetanilide, then
0.7 g of sulfamic acid and the nonionic surfactant in an amount as
identified in Table 1 were added, and 100 g of ice was added to cool the
mixture and obtain a coupling solution. To the coupling solution thus
obtained, the diazotized solution obtained by the above diazotization
reaction, was dropwise added over a period of one hour at a temperature of
from -2.degree. to +2.degree. C. During this period, 370 g of ice was
further added. Then, a coupling reaction was conducted for 3 hours while
adding 500 g of ice, to obtain a reaction mixture containing a compound of
the following formula:
##STR10##
Then, the temperature was raised to the predetermined heat treatment
temperature as identified in Table 1 over a period of 2 hours, whereupon
heat treatment was conducted at the same temperature for a period of time
as identified in Table 1. Immediately thereafter, the mixture was filtered
by a Nutsche funnel and washed with water. With respect to a cake thus
recovered, the yield and the volume of the cake was measured. The results
are shown in Table 1.
TABLE 1
__________________________________________________________________________
Cake
Amount
Temp.
Time
volume
Yield
Filtration
No Nonionic surfactant
HLB
(g) (.degree.C.)
(hr)
(ml/g)
(%) speed
__________________________________________________________________________
Example
1 Polyoxyethylene-9-
14 4.5 60 1 2.3 93.0
Very quick
octadecenoic acid ester
2 Polyoxyethylene-9-
14 3.0 55 1.5
2.4 92.2
Very quick
octadecenoic acid ester
3 Polyoxyethylene-9,12-
15 4.0 60 1 2.5 92.3
Very quick
octadecadienoic acid ester
4 Polyoxyethylene
12 5 60 1 2.4 91.7
Very quick
octadecanoic acid ester
5 Polyoxyethylene dodecanoic
13 6.0 50 2 2.8 92.0
Very quick
acid ester
6 Polyoxyethylene-9-
12 4.0 65 1 2.5 92.1
Very quick
octadecenoic acid ester
Compara-
1 Nil Nil 60 1 5.7 91.8
Very slow
tive 2 Polyoxyethylene lauryl
14 4.5 60 1 3.2 85.2
Quick
Example ether
3 Polyoxyethylene
14 4.5 60 1 3.1 81.5*
Quick
nonylphenyl ether
__________________________________________________________________________
*Substantial foaming observed during the coupling reaction.
TEST EXAMPLES 1 and 2
(Stability with time)
To evaluate the stability with time as a disperse dye, the following test
was conducted with respect to each of the cakes obtained in Example 1 and
Comparative Example 2.
Water was added to the wet cake (25 g as solid content), 16 g of Reax
85A.RTM. (a lignin type dispersing agent, manufactured by Westvaco
Company, U.S.A.) and 6 g of Diadisperse.RTM. SW (Tamol type dispersing
agent, manufactured by Mitsubishi Kasei Corporation) to bring the total
amount to 500 g. This mixture was introduced into a 1 l vessel of a six
cylinder type grinder (pulverizer) Model 6TSG, manufactured by AIMEX Co.,
Ltd., and 500 ml of glass beads of from 0.8 to 1.2 mm were added thereto,
and the mixture was pulverized at a high speed of 1500 rpm until the
average particle size of the dye became at most 1 .mu.m. Then, the dye
dispersion and the glass beads were separated by filtration. The dye
dispersion was dried by an atomizer, manufactured by NIRO Company to
obtain a powder of a disperse dye composition.
Instead of examining the stability with time at room temperature, a part of
the powder was sealed in a glass bottle and maintained at 60.degree. C.
for 3 days to conduct an accelerated test.
The dispersibility of the powder before and after the accelerated test was
evaluated as follows. Into a 150 ml polyethylene beaker, 1 g of the
disperse dye composition powder and 99 ml of water were introduced and
thoroughly stirred by a stirrer to obtain a uniform dispersion. Then, 100
ml of the disperse dye dispersion was filtered under suction at a reduced
pressure of 150 mmHg (2.0.times.10.sup.4 Pa) by a filter paper 5 c (7 cm
in diameter) manufactured by Toyo Filter Paper Company, whereby the time
(sec) for filtration was examined. The results are shown in Table 2.
TABLE 2
______________________________________
Test Example 1
Test Example 2
______________________________________
Cake producing
Example 1 Comparative
process Example 2
Before the test
17 sec 18 sec
After the test
19 sec 55 sec
______________________________________
From the above results, it is evident that when a cake was prepared by heat
treatment by means of the polyoxyethylene-9-octadecenoic acid ester, the
cake had no problem with respect to the stability with time as a disperse
dye. On the other hand, when a cake was prepared by heat treatment by
means of the polyoxyethylene lauryl ether, the cake had a problem with
respect to the stability with time as a disperse dye.
COMPARATIVE EXAMPLE 4
In the method of Comparative Example 1, the reaction mixture after
completion of the coupling reaction, was once filtered and washed with
water, and the cake thus obtained was put into 1200 ml of water. Then, the
temperature was raised to 95.degree. C. over a period of one hour,
whereupon heat treatment was conducted at the same temperature for 5
hours. Then, after cooling to 80.degree. C., filtration and washing with
water were conducted under the same conditions as in Comparative Example 1
by means of a Nutsche funnel.
As a result, the volume of the cake was 4.7 ml/g, and the yield was 91.7%.
EXAMPLE 7
A monoazo compound cake of the following formula was prepared in the same
manner as in Example 1 except that in Example 1, 68 g of
2,4-dinitro-6-bromoaniline was changed to 56.3 g of
2,4-dinitro-6-chloroaniline. In this case, the volume of the cake was 2.5
ml/g, and the yield was 91.9%.
##STR11##
EXAMPLE 8
A cake was prepared in the same manner as in Example 1 except that in
Example 1, 4.5 g of polyoxyethylene-9-octadecenoic acid ester (HLB14) as a
nonionic surfactant, was added after conducting the coupling reaction
instead of adding it prior to the coupling reaction.
In this case, the volume of the cake was 3.5 ml/g, and the yield was 92.3%.
EXAMPLE 9
A monoazo compound cake of the following formula was prepared in the same
manner as in Example 1 except that in Example 1, 93.5 g of
N,N-bis(acetoxyethyl)amino-2-methoxy-5-acetanilide was changed to 97.2 g
of N,N-bis(acetoxyethyl)amino-2-ethoxy-5-acetanilide. In this case, the
yield was 91.8%, and the volume of the cake was 2.2 ml/g.
##STR12##
EXAMPLES 10 to 15 and COMPARATIVE EXAMPLES 5 to 7
Into a 200 ml glass-lined reactor equipped with a stirrer, 44.5 g of 98%
sulfuric acid and 46.6 g of 43% nitrosyl sulfuric acid were charged, and
40 g of 2,4-dinitro-6-bromoaniline was added thereto under stirring at a
temperature of from 20.degree. to 25.degree. C., whereupon a diazotization
reaction was conducted at a temperature of from 20.degree. to 25.degree.
C. for 3 hours.
Into a 3 l cylindrical beaker with a bottom area of 125 cm.sup.2, 800 ml of
water and 2.5 g of 98% sulfuric acid were charged, and 31.5 g of
m-(N,N-dimethylamino)acetanilide was added thereto under stirring at a
temperature of at most 10.degree. C.
Then, 0.7 g of sulfamic acid and a predetermined amount of the nonionic
surfactant as identified in Table 3 were added thereto. Then, 100 g of ice
was added thereto to cool the mixture and obtain a coupling solution. To
the coupling solution thus obtained, the diazotized solution obtained by
the above diazotization reaction, was dropwise added over a period of one
hour at a temperature of from -2 to +2.degree. C. During this period, 250
g of ice was further added. Then, a coupling reaction was conducted for 3
hours, while adding 420 g of ice to obtain a reaction mixture containing a
compound of the following formula.
##STR13##
Then, the reaction mixture was heated to the temperature as identified in
Table 3 over a period of 2 hours and heat-treated at the same temperature
for a period of time as identified in Table 3. Then, the mixture was
cooled to 50.degree. C. and then filtered and washed with water by means
of a Nutsche funnel. With respect to the cake thus recovered, the yield
and the volume of the cake were measured. The results are shown in Table
3.
TABLE 3
__________________________________________________________________________
Cake
Amount
Temp.
Time
volume
Yield
No Nonionic surfactant
HLB
(g) (.degree.C.)
(hr)
(ml/g)
(%) Remarks
__________________________________________________________________________
Example
10
Polyoxyethylene-9-
14 2.1 80 1 2.3 91.0
octadecenoic acid ester
11
Polyoxyethylene-9-
14 1.0 60 3 2.5 90.7
octadecenoic acid ester
12
Polyoxyethylene-9,12-
15 3.0 80 1 2.6 90.1
octadecadienoic acid ester
13
Polyoxyethylene
12 2.0 70 2 2.5 90.2
octadecanoic acid ester
14
Polyoxyethylene dodecanoic
13 3.5 80 1 2.7 89.7
acid ester
15
Polyoxyethylene-9-
12 2.1 70 2 2.4 90.4
octadecenoic acid ester
Compara-
5
-- Nil 80 1 5.9 89.7
tive 6
Polyoxyethylene lauryl
14 2.1 80 1 3.5 84.8
Example ether
7
Polyoxyethylene
14 2.1 80 1 3.4 79.2
**
nonylphenyl ether
__________________________________________________________________________
**Substantial foaming observed during the coupling reaction.
TEST EXAMPLES 3 AND 4
(Stability with time)
To evaluate the stability with time as a disperse dye, evaluation was
conducted in the same manner as in Test Examples 1 and 2 with respect to
each of the cakes obtained in Example 10 and Comparative Example 6.
However, the composition of the wet cake and the dispersing agent was
changed such that water was added to the wet cake (18 g as solid content),
24 g of Reax 85A.RTM. and 8 g of Diadisperse.RTM. SW to bring the total
amount to 500 g.
As a result, when the cake obtained in Example 10 was used as a disperse
dye, no deterioration was observed in the dispersibility even after the
accelerated test (Test Example 3). On the other hand, when the cake
obtained in Comparative Example 6 was used as a disperse dye,
deterioration was observed in the stability with time (Test Example 4).
COMPARATIVE EXAMPLE 8
In the method of Comparative Example 5, the reaction mixture after
completion of the coupling reaction, was once filtered and washed with
water, and the cake thus obtained was put into 1200 ml of water. Then, the
temperature was raised to 95.degree. C. over a period of one hour,
whereupon heat treatment was conducted at the same temperature for 5
hours. Then, after cooling to 80.degree. C., filtration and washing with
water were conducted under the same conditions as in Comparative Example 5
by means of a Nutsche funnel.
As a result, the volume of the cake was 4.9 ml/g, and the yield was 89.6%.
EXAMPLE 16
A monoazo compound cake of the following formula was prepared in the same
manner as in Example 10 except that in Example 10, 40 g of
2,4-dinitro-6-bromoaniline was changed to 33.2 g of
2,4-dinitro-6-chloroaniline. In this case, the volume of the cake was 2.4
ml/g, and the yield was 90.1%.
##STR14##
EXAMPLE 17
A cake was prepared in the same manner as in Example 10 except that in
Example 10, 2.1 g of the polyoxyethylene-9-octadecenoic acid ester (HLBl4)
as a nonionic surfactant, was added after conducting the coupling reaction
instead of adding it prior to the coupling reaction.
In this case, the volume of the cake was 3.5 ml/g, and the yield was 89.6%.
EXAMPLES 18 to 23 AND COMPARATIVE EXAMPLES 9 TO 11
Into a 300 ml glass-lined reactor equipped with a stirrer, 46 g of 98%
sulfuric acid and 60.8 g of 43% nitrosylsulfuric acid were charged, and
41.4 g of 2,6-dichloro-4-nitroaniline was added thereto under stirring at
a temperature of from 20.degree. to 35.degree. C., whereupon a
diazotization reaction was conducted at a temperature of from 30.degree.
to 35.degree. C. for 3 hours to obtain a diazotized solution.
On the other hand, into a 2 l cylindrical beaker with a bottom area of 125
cm.sup.2, 575 ml of water, 31.6 g of 98% sulfuric acid were charged, and
48.4 g of N-ethyl-N-(2-cyanoethyl)aniline was added thereto at a
temperature of at most 30.degree. C. Then, 1.6 g of sulfamic acid and a
nonionic surfactant as identified in Table 4 in an amount as identified in
Table 4 were added thereto, and 442 g of ice was added to cool the mixture
and obtain a coupling solution. To the coupling solution thus obtained,
the diazotized solution obtained by the above diazotization reaction, was
dropwise added over a period of one hour at a temperature of from
-5.degree. to +5.degree. C. Then, a coupling reaction was conducted at the
same temperature for one hour to obtain a reaction mixture containing as
the main component a monoazo compound of the following formula:
##STR15##
The reaction mixture was heated to a predetermined temperature as
identified in Table 4 over a period of one hour and then heat-treated at
that temperature for 2 hours. Then, the mixture was cooled to 40.degree.
C. and then filtered by means of a Nutsche funnel and washed with water.
With respect to a cake recovered by the filtration, the yield and the
volume of the cake were measured. Further, the foaming state during the
heat treatment was observed. The results are shown in Table 4.
TABLE 4
__________________________________________________________________________
Amount
Temp.
Time Cake volume
Yield
Nonionic surfactant
HLB
(g) (.degree.C.)
(hr)
Foaming
(ml/g) (%)
__________________________________________________________________________
Example 18
Polyoxyethylene-9-
14 2.2 80 2 Very little
1.88 98.1
octadecenoic acid ester
Example 19
Polyoxyethylene-9-
14 1.1 80 2 Little
1.93 98.0
octadecenoic acid ester
Example 20
Polyoxyethylene dodecanoic
13 3.5 60 1 Moderate
2.10 96.3
acid ester
Example 21
Polyoxyethylene
12 2.0 70 2 Little
1.92 96.5
octadecanoic acid ester
Polyoxyethylene-9,12-
Example 22
octadecadienoic acid ster
15 3.0 80 2 Little
1.89 97.1
Example 23
Polyoxyethylene-9-
12 2.0 80 2 Little
1.97 97.8
octadecenoic acid ester
Comparative
-- -- 80 2 Very high
3.22 96.1
Example 9
Comparative
Polyoxyethylene lauryl
14 2.2 80 2 High 2.02 90.9
Example 10
ether
Comparative
Polyoxyethylene
14 2.2 80 2 Moderate
2.36 80.2
Example 11
nonylphenyl ether
__________________________________________________________________________
TEST EXAMPLES 5 and 6
(Stability with time)
To evaluate the stability with time as a disperse dye, a test was conducted
in the same manner as in Test Examples 1 and 2 with respect to each of the
cakes obtained in Example 18 and Comparative Example 10.
As a result, when the cake obtained in Example 18 was used as a disperse
dye, no deterioration was observed in the dispersibility even after the
accelerated test (Test Example 5). On the other hand, when the cake
obtained in Comparative Example 10 was used as a disperse dye,
deterioration was observed in the stability with time (Test Example 6).
EXAMPLE 24
A monoazo compound cake of the following formula was prepared in the same
manner as in Example 18 except that in Example 18, 59.2 g of
2,6-dibromo-4-nitroaniline was used instead of 41.4 g
2,6-dichloro-4-nitroaniline, and the amount of
polyoxyethylene-9-octadecenoic acid ester was changed to 3 g.
##STR16##
As a result, foaming was very little, the volume of the cake was 1.95 ml/g,
and the yield was 97.8%.
EXAMPLE 25
An azo compound cake was prepared in the same manner as in Example 18
except that in Example 18, 2.2 g of polyoxyethylene-9-octadecenoic acid
ester (HLB14) as a nonionic surfactant, was added after the coupling
reaction instead of adding it prior to the coupling reaction, and foaming,
the volume of the cake and the yield were evaluated in the same manner. As
a result, foaming was little, the volume of the cake was 2.20 ml/g and the
yield was 96.2%.
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